Process for breaking petroleum emulsions



- procedures.

Patented July 18,1944

UNITED STATES PATENT OFFICE PROCESS FOR BRE EMUL Melvin De Groote, University City,

Keiser, Webster Groves,

, Petrolite Corporation, Ltd., Wilmington,

corporation of Delaware AKING PETROLEUM and Bernhard assignors to Del-, a

No Drawing. Application June 15, 1942 Serial No. 447,164

Claims. (Cl.

rapid process for separating emulsions which have been prepared under controlled conditions form mineral oil, such as crude petroleum and relatively soft waters or weak brines. Controlled emulsification and subsequent demulsification under the conditions just mentioned is of significant value in removing impurities, particularly inorganic salts, from pipeline oil.

We have discovered that if one oxyalkylates glycerol so as to introduce at least three 'oxyalkylene radicals for each hydroxyl group, and if the product so obtained is reacted with a polybasic carboxy acid having not over eight carbon atoms, and in such a manner as to yield a fractional ester, due to the presence of at least one free car-boxy] radical, one can then esterify said acidic material or intermediate product with at least one mole of an alcoholic compound of the type herein described to give a variety of new compositions of matter which have utility in the demulsification of crude oil.

The compounds herein contemplated may be produced in any suitable manner, but are usually manufactured by following one of two general In one of said procedures the oxyalkylated glycerol, which is, in essence, a polyhydric alcohol, is reacted with a polybasic acid so as to give an acidic material or intermediate product, which, in turn, is reacted with an alcoholic body of the kind hereinafter described, and momentarily indicated by the formula Rl(OH)m. Generically, the alcoholic body herein contemplated may be considered a member of the class in which m may vary from 1 to 10, although the specific significance of m in the present instance will be hereinafter indicated. The second procedure is to react an alcohol of the formula type R1(OH)m with a polybasic acid so as to produce an intermediate product, and then react said intermediate product or fractional ester with the selected oxyalkylated glycerol.

Glycerol may be conveniently indicated by the following formula:

If treated with an oxyalkylating agent, and motype indicated by the in which 11."

mentarily consideration will be limited to an oxyethylating agent, one may obtain an oxyethylated glycerol of the following formula type:

in which the value of n may vary from 3 to 10 and all the values of 11. need not be identical. If a polybasic carboxy acid be indicated by the formula:

COOK

COOH

thenthe acyclic reaction product of one mole of.

oxyethylated glycerol and one mole of a polybasic carboxy acid may be indicated by the following formula:

(C3H40).'00CR(C0OH)1|" CJHuOr-(CiHAOLuH (Calico) n'H has the value of one or two. Similarly, if two moles of the polybasic acid be used, then the compound may be indicated by the following formula:

(omiowoocmooomp- G$H6or( iH40)n' H)n" ((hHiOMH Likewise, if three moles of a polybasic acid are employed, the compound may be indicated by the following formula:

,or more moles of an alcohol of the kind previously described in a generic sense as Rl(OH)m, then obviously, one may obtain a material of the following formula:

CHOH OOCR a 4) include ethylene oxide, propylene oxide, butylene like.-

oxide and glycid,-which, although not included, strictly speaking, CnHnO, is included within the meaning of the hereto appendedclaims and may be-simply considered .as a variant of propylene oxide, 1. e., hydroxypropylene oxide. Similarly, where a carboxylic hydrogen atom appears, it may be replaced by metaLan ammonium radical, or substituted ammonium radical, or by an organic group derived from an alcohol, such as an aliphatic alcohol, an aralkyl alcohol, or an alicyclic alcohol. It may also be converted into an amide, including a polyaminoamide. Thus, the preceding formula may be rewritten in its broadest scope, as follows: I

000111) z in which n replaces the numbers 2, 3 or 4, z in by the unitary structure cerned with materials of this type, it is so adopted here. Thus, reference in the appended claims to polymers is intended to include the self-esterificationproducts of the monomeric compounds.

In'view of what has been said, and in view of the recognized hydrophile properties of the renature. The compounds may vary from monocludes the acidic'hydrogen atom itself. In the above formula,and hereafter for convenience, R1 is intended to include any hydroxyl groups that remain, A w

If the compounds herein contemplated are obtained under usual conditions, at the lowest temperatures, then the monomeric form is most likely to result,

The production of the-compounds herein contemplated is the result of one or more esterification steps. As is well known, esterification procedures can be carried out in various manners, but generally speaking, esteriflcations can be carried out at the lowest feasible'temperatures by using one or several procedures. One procedure is to pass an inert dried gas through the mass to be festerifled, and have present at the same time-a small amount of a catalyst, such as dried H Cl gas, a dried sulfonic acid, or the Another and better procedure, in many instances, is to employ the vapors of a suitable liquid, so as to remove any water formed and condense both the vapors of the liquid employed and the water in such a manner as to trap out the water and return the liquid to the reacting vessel. This procedure is commonly employed in thearts, and for convenience, reference is made to U. S. Patent No. 2,264,759, dated December 2, 1941 to Paul C. Jones.-

Referring again to the last two formulas indicating the compounds under consideration, it can be readily understood that such compounds, in numerous instances, have the property of polyfunctionality. In view of this fact, where there is at least one residual carboxyl and at least one residual hydroxyl, one would expect that under suitable conditions, instead of obtaining the monomeric compounds indicated, one would, in reality, obtain a polymer in the sense, for exmers to polymers, in which the unitary structure appears a number of times, for instance, 10 or 12 times. It is to be noted that true resins, i. e., truly insoluble materials of a hard plastic nature, are not herein included. In other words, the polymerized compounds are soluble to a fairly definite extent, for instance, at least 5% in some solvents, such as water, alcohol, benzene, dichloroethyl ether, acetone, cresylic acid, acetic acid, ethyl-acetate, dioxane, or the like; Thisis simply another way of stating that the polymerized product contemplated must be of the sub-resinous type, which is commonly referred a to as an A resin, or a B resin, as distinguished ample, that polyethylene glycols represent a the monomeric compounds, but since, for all practical purposes, they can be so indicated, and since such practice is common in the arts conclaims the word "polar" from a C resin, which is a highly infusible, insoluble resin (see Ellis, Chemistry of Synthetic Resins (1935), pages 862, et seq.). i

Reviewing the form as presented, it is obvious that one may obtain compounds within the scope disclosed, which contain neither a free hydroxyl nor a free carboxyl roup, and one may also obtain acompound of the type in which there is present at least one free carboxyl, or at least one free hydroxyl, or both. The word polar has sometimes been used in the arts in this particular sense to indicate the presence of at least one free hydroxyl group, or at least, one free carboxyl group, or both. In the case of the free carboxyl group, the carboxylic hydrogen atom may, of course, be replaced by any .ionizable hydrogen atom equivalent, such, for example, as a metal, .an ammonium radical, a substituted ammonium radical, etc. In the hereto appended is used in this specific sense. f

We are aware that compounds similar to those contemplated in the present instance maybe derived from polyhydroxylated compounds having more than three hydroxyl groups. For instance, they may be derived from acyclic diglycerol, triglycerol, tetraglycer'ol, mixed polyglycerols, mannitol. sorbitol, various 'hexitols, dulcitol, pentaierythritol, sorbitan, mannitan, dipentaerythritol monoether, and. other similar compounds. Such particular types in which higher hydroxylated materials are subjected to oxyalkylation and then employed in the same manner as oxyalkylated glycerol, is employed in the present instance, are not contemplated in this specific case, although attention is directed to the same.

; Reference is also made to other oxyalkylated I compounds which may be used as reactants to replace oxyalkylated glycerol, or oxyalkylated ethylene glycol, which latter reactant is described original hydroxyl group.

than three hydroxyl groups. For instance, the oxyalkylated derivatives, particularly the oxyethylated derivatives of ethyldiethanolamine. bis(hydroxyethyl)acetamide, the acetamide of trls(hydroxymethyl) aminomethane, .tetrahy droxylated ethylene diamine, etc. Compounds may also be derived, from cyclic diglycerol and the like.

Furthermore, for convenience, attention is dicated in the following three examples, is substantially identical with that outline in said 7 aforementioned German patent.

directed to a somewhat similar class of materials 10 which are described in our co-pending application Serial No. 401,380, filed .July 7, 1941, now Patent No. 2,324,492, dated July 20, 1943. Said co-pending application involves the use of the same type of alcoholic bodies for reactants, but

Oxxamxmrsp Gn'rozsor. Example 1 184 pounds of glycerol is mixed with /z%, by weight, of caustic soda ,solution having a specific gravity of 1.383. The caustic soda acts as a catalyst. The ethyleneoxide is added in relatively small amounts, for instance, about 44 pounds at a time. The temperature employed is from 150-180 C. Generally speaking, the

gauge pressure during the operation approximates 200 pounds at the maximum, and when reaction is complete, drops to zero, due to complete absorption of the ethylene oxide. When all the ethylene oxide has been absorbed and the reactants cooled, a second small portion, for intwo, or three, or more, might be introduced;

phthalic. Similarly, one may employ acids such as fumaric, glutaconic, and various others, such as citric, malic, tartaric, and the like. The selection ofthe particular tribasic or dibasic acid employed, is usually concerned largely with the convenience of manufactureof the finished ester,

and also the price of the reactants. Generally speaking, phthalic acid or anhydride tends to produce resinousmaterials, and greater care must be employed if the ultimate or final product be of a sub-resinous type. Specifically, the preferred type of polybasic "acid is such as to contain six carbon atoms or less. Generally speaking, the higher the temperature employed, the easier it is to obtain large yields of esterified product, although polymerization may be stimulated. Oxalic acid may be comparatively cheap. but it decomposes readily at slightly above the boiling point of water. For this reason it is more desirable to use an acid which is more resistant to pyrolysis. basic acid is available in the form of an anhydride, such anhydride is apt to produce the ester with greater ease than the acid itself. For this reason, maleic anhydride is particularly the cost is comparatively low on a per molar basis, even though somewhat higher on a per pound basis. vSucclriic acid or the anhydride has many attractive qualities of maleic anhydride,

Similarly, when a polyadaptable, and also, everything else considered,

and this is also true of adipic acid. For purposes of brevity, the bulk of the examples, hereinafter illustrated, will refer'to the use of maleic anhydride, although it is understood that any other suitable polybasic acid may be employed. Fur-.

thermore, reference is made to derivatives obtained by oxyethylation. although, as previously pointed out, other oxyalkylating agents may be I employed. I

As far-as therange of oxyethylated glycerols employed as reactants is concerned, it is our 5 preference to employ those in which approximately 15 to 24 oxyethylene groups have been introduced into a single glycerol molecule. This means that approximately five to eight oxyethylene radicals have been introduced for each The oxyalkylation of glycerol is a well'known procedure (see Example ll of German Patent No. 605,973, dated November 22, 1934, to I. G. Farbenindustrie Akt. Ges.)

The procedure in- 76 stance, 44 more pounds of ethylene oxide, are added, and the procedure repeated until the desired ratio of 15, pound moles of ethylene oxide to one pound mole of glycerol is obtainedfThis represents 660 pounds of ethylene oxide for 192 pounds of glycerol.

OXYETHYLATED GLYCsaoL Example 2 The ratio of ethylene oxide is increased to 18 pound moles for each pound mole of glycerol.

Otherwise, the same procedure is followed as .in-

Example 1, preceding.

OxYE'rr-rYLA'rEo GLYCEROL Example 3 The same procedure is followed as in the two previous examples, except that th ratio of ethylene oxide to glycerol is increased to 21 to one.

OxYE'rHYLA'rsn GLYcaRoL Manners Ewamplel One pound mole of oxyethylated glycerol (1 to 15 ratio) prepared in the manner previously described is treated with one pound mole of maleic anhydride and heated at approximately C.

for approximately thirty minutes to two hours, with constant stirring, so as to yield a monomaleate.

OxYE'mxLArEn GLYCEROL MALEA1E Example 2 Th same procedure is followed as in the preceding example, except that two moles of maleic anhydride are employed so as to obtain the dimaleate instead of the monomaleate.

OXYETHYLATED GLYCEROL MALEATE Example 3 The same procedur is followed as in the two preceding examples, except that three moles of maleic anhydride are employed so as to obtain the trimaleate.

OXYETHYLATED' GLYCEROL MALEATE Example 4 The same procedure is employed as in the preceding examples, except that oxyethylated glycerol (ratio 1 to 18) is substituted in'place of oxyethylated glycerol (ratio 1 to 15).

made to the following examples.

Example 2, preceding.

oxmrnvtiiran Gmcrmor. Mum-r:

Example The sam procedure is employed as in the preceding examples, except that oxyethylated glycerol (ratio 1 to'21) is employed instead of oxyethylated glycerol (ratio 1 to 15) or (1 to 18).

Previous reference .has been made to an alcoholic body which has been, defined generically by the formula R1(OH) .m. The sub-generic class 01 alcoholic compounds employed as reactants in the manufacture of the present compounds, are hydroxylated substituted pyridiniumhalides or other compounds in which there is present an anion functionally equivalent to the halide amine, i. e., an anionic functional equivalent to the chloride or bromide ion. There is a larg variety of such compounds available, and they are characterized by the fact that the group substituted forthe hydrogen atom of the pyridinium radical,

'as part of a hydroxy hydrocarbon radical, or it may be present as the part 0t an acyl radical. For instance, it may be'presen't .as part of a ricinoleyl radical, or similar radical, derived from hydroxy-stearic acid or the like.

In order to illustrate suitable quaternary reactants ofthe type above described, reference is that this list is Who meansexhaustive.

1 Inrsiwranmrn Rnac'rem.

Example 1 500 g. of a fatty acid ethanolaniide, obtained lution. 'After being separated from the primary compounds not reacted upon, the mixture of pyridinium-, piscolinion-fand othe pyridinium compounds obtained,

homologous ay be further worked up to form a watery solution.

When working at 150-160", the reaction is more 1 rapid.

Furthermore, pure pyridine may be used instead of a mixture of pyridine bases.

,(Comparefwith Example 2.. oi the aforementioned Haa'ck Patent No. 2,242,211)

I INTERMEDIATE Rnlicrm'r Example. 2'

Hydroxyethyl ricin'oleoamide derived by reaction between ricinoleic acid and monoethanolamine is substituted for the amide employed in It is to be noted I Imnnmmmri: Rmcrlin'r Example 3 A drastically oxidized castor oil having approximately the following characteristics:

Acid number 13.2 to 25.0 Saponiflcation number 230.5 to.2'74.0 Iodine number -Q 43.5to 55.0 Acetyl number 164.0 to 192.0 Hydroxyi value 188.0 to 220.0 Percent unsaponifiable matter 1.1 Percent nitrogen r 0.0 Percent S03 0.0 Percent ash Trace is converted into the hydroxyethyl amide by reaction with monoethanolamine. substituted for the amide employed in Example 1, preceding.

INTERMEDIATE Rnacrm'r Example 4 One pound-.mole of castor oil is treated with three pound moles of ethylene oxide at a temperature of 100-200 C. at a gauge pressure of 100 pounds and less than 300 pounds, so-as to pro-- duce an oxyethylated triricinolein. The product so obtained isconverted into an amide in the same manner as described underthe heading Intermediate reactant, Example 1," preceding.

, Such amide is employed instead of the amide v by reaction of split cocoanut oil (containing all the natural acids, beginning with the caprylic up only a trace of the free base.

amples ar substantially as they appear, numdescribed in Example 1, preceding.

INTERMEDIATE Rniicrenr Example 5 Phenylstearic acid is prepared in any suitable manner, as, for example, in-the manner described in U. S. Patent No. 2,081,075, dated May 18, 1937, to Vobach. This is converted into phenylstearic hydroxy ethyl amide, and such amide employed in the manner described "in Example 1, preceding.

The manufacture of the above compounds is usually conducted with an excess of the pyridinium-base halide, such as th hydrochloride or hydrobromide, and usually in the presence of a significant amount ofthe free pyridinium base itself. In many instances, however, there is no need to use an excessof the pyridinium base halide, and in fact, no need to have present any of the free'pyridinium baseitself, or at the most,

(The above 5 exbered Examples 1 through 5, in our co-pending application Serial NO.-401,375, filed July'l, i941.

INTERMEDIATE REACTANT Example 6 8 parts of chloracetyl chloride were added slows 1y to 20 parts of castor oil, while stirring. After the first vigorous reaction had subsided, the mix- The productwas a red, viscous .oil which was.-

nearly solidat room temperature. Inwater it formed a clear, viscous solution of low surface tension. The product was not precipitated from solution by alk salts. I

Such amide is 1i, alkaline earth-, or heavy metal reactant,

InTEamEnmrE REAcTm Example 7 12 parts or chloracetyl chloride were added with stirring to 90 parts of castor oil. The mixturewas warmed on the steam plate for 1 4 hours, purged of H01 with dry air, and then mixed with 8 parts of pyridine. This mixture was left on the steam plate over night. The product was a dark red oil, dispersible in water, and solublein xylene. At least a predominaniPportion of this material consisted of a quaternary ammonium salt having the formula:

C6 Jl-H-cHlI "c 0 0-0 H: ctmr-cnon-cmnw-mo 0 n CaHrr-CHOH-CmHn-C O O- Hg INTERMEDIATE REACTANT Example 8 Bis(hydroxyethyl) ricinoleoamide is substituted for castor oil in the preceding example so as to give a suitable monopyridinium derivative.

INTERMEDIATE "Rmcrnnr Example 9 Monoricinolein is substituted for castor oil 111 Intermediate reactant, Example 7,. preceding. so as to yield the monopyridinium derivative.

INTERMEDIATE REAcTAm' Example 10 Diricinolein is substituted for monoricinolein in the preceding example.

' INTERMEDIATE REAcTmT sam le 11 The ricinoleoaniide derived from tris(hydroxymethyl) aminomethane is substituted for blSi' Yf droxyethyl) ricinoleoamide in Intermediate reactant, Example 8, preceding.

INTERMEDIATE Rnecrsrzr Example 12 The neutralester derived by esterifying one part of diethylene glycol with2 parts of ricinoleic acid; is substituted for castor oil in Intermediate Example '1, preceding, so as to yield the monopyridinium derivative. I Inrnsmromrs Rrac'rm Example 13- f Mannitan monooleate is substituted for castor oil in Intermediate reactant, Example 'L'so as to obtain the monopyridinium derivative.

:Inraamnnmrn RnecTAm Exam l 14' decane may be employed.

lineman-r: Rucrsn'r Example 15 Phenol is reacted with acetone (or diethyl iretone or methyl ethyl ketone), as described in U." S. Patent No. 1,225,748, to Wallace A. Beatty. to give the compound diphenylol methane.

CHI duHcOH c on. cinion (or the,corre'sponding diethyl or methyl ethyl compound). This compound is hydrogenated as described in British Patent No. 274,439, to give the corresponding dicyclohexylol dialkyl methane. The product so obtained may be conveniently considered as a dial and substituted in place of the diol used as a reactantin Intermediate reactant, Example 14, preceding.

Preceding Examples 6 and 7 are substantially as they appear inthe co-pending applicat on of Charles N. Blair, Jr., Serial No. 353,127, filed August 17, 1940, now Patent No. 2,306,775, dated Dec. 29, 1942, as'Examples 1 and 2. Compare Intermediate reactant, Examples 8 -15, inclusive. with'lntermediate reactant, Examples 6 and '1. Note also that a somewhat similar reactant, which may be employed in the manufacture of intermediates by the same procedure, is obtained by reacting two moles of ricinoleic acid with one mole of ethylene diamine, or one mole of ricinoleic acid with one mole of hydroxyethyl ethylene,

diamine to give an amide.

ImEanEnmTE Rreorm Example 16 The procedure described in the aforementioned Blair application Serial No. $53,127 is followed so as to give a chemical compound analogous to the one depicted by structural formula in Intermediate reactant, Example '7, preceding exoept that sufflcient chloracetyl chloride, and likewise, sufllcient pyridine, is employed so that a dipyridinium compound is obtained Immature Runn ng- 7 Example 17 12 parts of ricinoleo-hydroxymethylamide, 8

\ parts of anhydrous pyridine hydrochloride; and

20 parts ofpyridine are stirred together at 70-80 C. until a test sample of the reaction mixture dissolves in water to give clear solutions. The reaction mixture is then distilled at (iii-70 C. under reduced pressure to remove pyridine.

' Acetone is then added to the distillation residue,

which is a viscous mass, whereby the new quaternary salt is precipitated in the form of white needles. The new quaternary .salt, ricinoleomethyl pyridinium' chloride, thus obtained when purified, if necessary, by recrystallization from acetone, gives analyses corresponding to the for- The new quaternary salt is readily soluble in warm water to give clear foaming solutions.

(Compare with Examplez of U; 8. Patent No.

2,146,392, dated February'l, 1939, to Baldwin and mula type:

maximum REAcTA T Ex mple 18 U. 'sr'eteint N6.. '2,14s',4oa, dated February 7,

1939, to Shipp; discloses compounds of the following type formula: r"

Obviously, a compound of the above type or a INTERMEDIATE REACTANT Example 23 As to other substituted pyridinium type compounds which may serve as reactants, in the manufacture of the compounds of the kind herein contemplated, reference is made to the following:

U. S. Patent No. 2,189,397, February 6, 1940, to Harris; 2,189,664, February 6, 1940, to Katzman; 2,190,133, Februarylii, l940,to Epstein et al.;

- 2,213,979, September 10, 1940, to Epstein et al.;

suitable variantrthereof' may have present an 7 alcohol hydroxyl group. For instance, R may be derived from ricinoleic acid. Such compound. may be treated with ethylene oxide so as to convert the amino hydrogen atom into a hydroxy- The same sort or procedure enumerated in the preceding example may be used to assure the presence 015 an alcoholic hydroxyl group.

INTERMEDIATE RmcTA T Example 20 Compounds are-obtained comparable to those described in Examples 1-5, inclusive, by use of diethanolamine, instead of monoethanolainine for the production of amide or by oxyethylation or oxyalkylation or the completed product derived,

from monoethanolamine, whereby an amino hydrogen atom is-converted into a, hydroxyethyl group. v INTERMEDIATE REAcTANT e 21 An esterifled tertiaryamine, such as ethyl diethanolamine or triethanolamine, as exemplified by the following formula: I

' accoun- OIICaHa-N oneim in whichRCO-is a ma acid radical, such as the oleic acid radical or ricinoleic acid radical, is subnov stituted for the hydroxylated amide in the type of material exemplified by Exad1ples1-5, preceding.

INTEnMEoIATE REAC'IAN'I' Example 22 An esterifled polyamine of the following forizeocem clnlou I CiHiOCaHi OHCQH CzHaOH is substituted for the somewhat analogous mono amino reactant of the-preceding example.

and 2,217,683, October 15, 1940, to Katzrnan.

. INTERMEDIATE REACTANT Example 24 Abighmolal amine, for instance, the "amine derived by converting oleic. acid, stearic acid, ricinoleic acid, lauric acid, and the like, into the corresponding amide, and then reducing to the nitrile and then further reducing'to the amine, is

treated with an'oxyalkylating agent, such as ethylene oxide, to give a product suchas hydroxyethyl dodecylamine, or his (hydroxyethyl) dodecylamine. Such products are then treated with pyhydrochloride or the equivalent in the manner contemplated in Intermediate reactant, Examples 1-5, preceding, so as to droxylated compound.

INTERMEDIATE REACTANT Example 25 The ricinoleic acid' amide derived by reaction between ricinoleic acid and tris(hydroxymethyl) aminomethane is reacted .u'r ith' pyridine hydro chloride in the manner illustrated by Intermediate reactant, Examples 1-5, preceding.

INTERMEDIATE REACTANT- Ezamplezb 2-amino-2 methyl-1-propanol is reacted with ricinoleic acid and the amide so obtained reacted with pyridinejhydrochloride in the manner exemplified by Intermediate reactant, Examples l-5, I

preceding;

Similar reactants include the following: 2- amino-l-butanol; Z-amino-Z-methyh1,3e-propane diol; 2-amino-2-ethy1 13epropane diol; 1-3-diamino propanol. Such materials may not only be combinedwith ricinoleic acid; but in such instances where there is more than one available hydroxyl radical after completion of the intermediate, onemay use oleic or naphthenic acid or the like to introduce a high molal acyl group.

It is to be noted that some of the pyridinium com-' pounds above described as reactants represent: new compositions or compounds. Similarly, analogous materials so derived that there .is no residual alcoholic hydroxyl, also represent new types of materials.

- CoMrLEI-EnMoNoMER'Ic D nIvArIvE Ea:ample 1 One pound mole of a product of the kind'described under the heading Oxyethylated 'g cerol maleate, Example 1 is reacted with one ound mole of Intermediate reactant, Example 6, preterably in the absence of any high boiling hydrocarbon or inert solvent. However, if an inert vaporizing solvent is employed, it is generally necessary to-use one which has a higher boiling range than xylene, and sometimes removal of such sol- I vent might present a diflicultyl In other instances, however,- sucifhigh boiling inert vaporizing solvent, if employed, might bepermitted to yield a hyassavov remain in the reacted mass and appear as a constituent or ingredient of the final -product. In

any event, our preference is to conduct the reaction in the absence of any such solvent and permit the reaction to proceed with the elimination of water. The temperature of reaction is about 180 to 200 C. and time of reaction about 20 hours.

Comtarsp Monomuuc Dsluvarrva Example 2 Comma-ab MONQMERIC DERIVATIVE Example 3 The same procedure is followed as in the two preceding examples, except that the trimaleate is substituted for the monomaleate or dimaleate in the two preceding examples.

Courmrsn MONOMERIC DERIVATIVE Example 4 The same procedure' is-followed as in Examples 2 and 3, immediately preceding, except that for each pound mole of the maleate, or each pound mole of the trimaleate, instead of using one pound mole of Intermediate reactant, Example 6, as a reactant, one employs two pound moles.

Comrnsrrn Monomer arc Daxrvsrrva Example 5 The same procedure is followed as in Exampled, preceding, except that for each pound mole of is the compound derived by reaction between pyridin hydrochloride and bis(hydroxyethyl) 'ricinoleoamide obtained in turn by reacting ricinoleic acid with diethanolamine.

COMPLETED Monommrc Dniuva'rrva Example The same procedure is followed as in Examples 1 to '7, preceding, except, that instead of employing Intermediate reactant, Example 6, one employs instead the compound obtained by reaction between pyridine hydrochloride and the ricinoleoamide of tris (hydroxymethyl) aminomethane.

The method of producing such fractional esters is wel1 known. The general procedure is to employ a temperature above the boiling point of water and below the pyrolytic point of the. reactants. The products are mixed and stirred constantly during the heating and esteriflcation step. If desired, an inert gas, such as dried nitrogen ordried carbon dioxide, may be passed through the mixture. Sometimes it is desirable "to add an esterification catalyst, such as sulfuric acid, benzene sulfonic acid, or the like. This is the same general procedure as employed in the manufacture of ethylene glyco1 dihydrogen diphthalate. (See U. S. Patent No.,2,075,107, dated March 30, 1937, to Frasier.)

Sometimes esteriflcation is conducted most readily in the presence of an inert solvent, that carries away the water of esterlflcation which maybe formed, although as is readily appreciated, such water of esteriiication is absentwhen such type of reaction involves an acid anhydride, such as maleic anhydride, and a glycol. However, if

, water is formed, for instance, when citric acid is trimaleate, instead of adding one pound mole of Intermediate reactant, Example 6,0ne adds three pound moles of Intermediate reactant, Example 6, for reaction.

co urtaran MONOMERIC DaarvArrva Example 6 Reference to the preceding examples will show that in each and every instance oxyethylated v glycerol (ratio 1 to has been employed as a raw material or primary reactant. In the present instance, a more highly oxyethylated glycerol is employed, to wit, one involving the ratio of 1 to 18. (See Oxyethylated glycerol maleate, Example 4", preceding.)

Comnnarsn Mononrsmc Drzruvarrva l Example 7 Catamaran MoxomaarcDauvArrva Example 8 The same procedure is followed as in Examples 1 to 7, preceding, except that Intermediate reactant'. Example 7 is substituted for Intermediate reactant, Example 6.

COmPLETEli Moxormarc Dsarvarrva Example 9 The'same procedure is followed as Examples 1 to 'l, preceding, except that the alcoholic body employed, then a solvent such as xylene may be present and employed to carry off the water found. The mixture of xylene vapors and water vapors can be condensed so that the water is separated. The Xylene is then returned to the reaction vessel for further circulation. This is a conventional and well known procedure and requires no further elaboration.

In the previous monomeric examples there is a definite tendency, in spite of precautions, at least in a numbenof instances, to obtain polymeric materials and certain cogeneric by-,=products. This is typical, of course, or organic reactions of this kind, and as is well known, organic reactions per se are characterized by the fact that 100% yields-are the exception, rather than the rule. and that significant yields are satisfactory, especially in those instances where the byproducts or cogeners may satisfactorily serve 'with the same purpose" as the principal or intentional product. This is true in the present instance. In many cases when the compound is manufactured for purposes of demulsiiication, one is better oil to obtain a polymer in the sense previously; described, particularly a polymer whose molecular weight is a rather small multiple of the molecular weight of the monomer, for instance, a polymer whose molecular weightis two, three, four, five, or six times the molecular weight of the monomer. Polymerization is hastened by the presence of an alkali, and thus, in instances where it is necessary to have a maximum yield of the monomer, it may be necessary to take such In the preceding examples of the Completed monomeric derivative, Examples 1 to 10, inclusive, no reference is made to the elimination of such alkaline catalyst, in view of the effectiveness of 'the low multiple polymers as demulsiflers. Previous reference has been made to the fact thatthe carboxylic hydrogen-atom might be variously replaced by substituents, including organic radi vlous that what has been previously said as to polymerization, with the suggestion that byproducts or cogeneric materials were formed, may be recapitulated with greater definlteness, and one can readily appreciate thatithe formation of heat-rearranged derivatives or compounds must take place to a greater or lesser degree.

' Thus, the products herein contemplated may be characterized by being monomers of the type previously described", or esterification polymers, or the heat-rearranged derivatives of the same, and thus including the heat-rearranged derivatives of 'both the polymers and the esterification monomeraseparateIy and jointly. Although the class of materials specifically contemplated in this in-.

stance is a comparatively small and narrow class of a broad genus, yet it is obviously impossible to present any adequate formula which would contemplate the present series in their complete ramification, except in a manner employed in the hereto appended claims. f p

3 Although the products herein contemplated vary so broadly "injtheir characteristics, i. e., monomers through sub-resinous polymers, soluble products, water-emulsiflable oils or compounds, hydrotropic materials, 'balsams, subresinous materials, semi-resinous materials, and; the like, yet there is always present the characteristic unitary hydrophile structure related bacl; to the oxya'lkylation, particularly the oxyethylation of the glycerol used as the raw material. As hereinafter indicated, in the resolution of oil field emulsions, the demulsifier may be .added to the emulsion-at the ratio of 1 part in 10,000, 1 part in 20,000, 1 part in 30,000, or for that matter, 1 part in 40,000. In such ratiosito5 well may be thatone can not differentiate be- I tween the solubility of a compound completely Soluble in water in any ratio, and a semi-resinous product apparently insoluble inwater in ratios by which ordinary insoluble materials are characterized. However, at such ratios the-importance must reside in interracial position and the ability to usurp, preempt, or replace the interfacial position previously occupied perhaps by the emulsify lng colloid. In any event; reviewed in this light, the obvious common property running through the entire series, notwithstanding variation in molecular size and physical make-up, ,is absolutely apparent. Such statement is an obvious over-simplification of the rationale underlying "demulsiflcation, and does not even consider the resistance. of an interracial film to crumbling;

displacement, being forced into solution, altered wetability, and the like. As to amidification polymers, for instance, where Z is a polyaminoamide radical, see what is said subsequently.

COMPLETED POLYMERIC DERIVATIVES INCLUDING HEAT-REARRANGED COGENERS Example 1 One selects apolyfunctional monomer of one of the types described underthe heading Completed monomeric derivatives, Examples 1 to 'l, and heats the same at ,a temperature of 220-240 C., with constant stirring, for a period of 2 to 60 hours, so as toeliminate sufficient water, in order to insure that the resultant product has a molecular weight approximately twice that of the initial monomer.

COMPLETED POLYMERIC DERIVATIVES. INCLUDING I HEAT-REnRRdNGED COGENERS Ewam'ple 2 The sameprocedur is followed as in the preceding example, except that polymerization is continued, using either a somewhat longer reaction time, or'-.it may be, a somewhat higher temperature, or both, so as to obtain a material having a molecular weight of approximately three to four times'that of the initial product.

COMPLETE: POLYMERIC Drluvarrvizs Incnvnmc Hsar-Rmnamcan Cocamm's Example 3 v The same procedure is followed as in Examples 1 and 2, preceding, except that one selects the polyfunctional monomerfrom one of the materials described under theheadings Completed monomeric derivative, Examples 8 to 10."

COMPLETED Pomm'anrc DExIva'rIvEs. INCLUDING Hear-Resumes!) COGENERS Example 4 The same procedure is followed as in Examples 1 to 3, preceding; except that one polymerizes a mixture instead of a single monomer, for instance, a. mixture of materials of the. kind described in Completed monomeric derivative, Ex-

ample 3, and in Completed monomeric deriva-,

tive, Example 4, are mixed in molecular'proportion and subjected to polymerization in the manner indicated in the previous examples.

It isunderstood, of course, that the polymerized product need not be obtained as a result of a two-step-procedure. m 'otherwords, one need not convert the reactants into the monomer and their subsequently convert the monomer .into the' polymer. through the monomer to the polymer in one step. Indeed, the formation of the monomer and polymerization maytake place simultaneously. This is especially true if polymerization is conducted in the absence of a liquid such as xylene, as previously described; and if one uses a comparatively higher temperature, for instance, approximately 220 C; for polymerization. Thus, one

.pound mole of an ,oxyethylated glycerol polymaleate of the kind described is mixed with one pound mole of a product of the-kind described v under the heading Intermediate reactant, Ex-

ample 7, and reacted 'for 20 hoursatapproxh mately 220 C., until the mass is homogeneous.

It is stirred constantly, during-reaction. Poly- The reactants may be convertedfunctionality may reside in dehydration (etheri- 'zation) of two hydroxyl groups attached to disgive a homogeneous mixture, then early in the reaction stage there is formed, to a greateror lesser degree, sufllcient monomeric materials so that a homogeneous system is present. quently, as reaction continues, the system may become heterogeneous andexist in two distinct phases, one being possibly an oily body of moderate viscosity, and the other being a heavier material, which is sticky or sub-resinous in nature. In many instances it will be found that the thinner liquid material is a monomer and the more viscous or resinous material is a polymer, as previously described. Such product can be used for demulsiiication by adding a solvent which will mutuallydissolve the two materials, or else, by separating the two. heterogeneous phases and employing each as if it were a separate product of reaction.

Conventional demulsifying agents employed in the treatment of oil field emulsions are used as Subse-' at a somewhat lower cost than is possible with other available demulsifiers, or conventional mixtures thereof. It is believed that the particular demulsiiying agent or treating agent herein described will flnd comparatively limited application, so far as the majority oi oil field emulsions are concerned; but we have found that such a demulsiiying agent has commercial value, as it will economically break or resolve ,oil field emulsuch, or after dilution with any suitable solvent,

such as water; petroleum hydrocarbons such as gasoline, kerosene, stove oil, a coal tarproduct such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., may be employed as diluents. Miscellaneous solvents, such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petroleum, etc., may be employed as diluents. Similarly, the material or materials herein described, when employed as demulsifiers for waterin-oil emulsions, may be admixed with one or more of the solvents customarily used in connection with conventional demulsifying agents, provided that such compounds are compatible. They will be compatible with the hydrophile type of solvent in all instances. Moreover, said material or materials may be used alone, or in admixture with other suitable well-known classes of demulsifying agents.

It is well-known that conventional demulsiiy-' ins agents may be used in a water-soluble form, or in an oil-soluble form, or in a torm exhibiting both oil and water-solubility. Sometimes they may be used in a form which exhibits relatively limited oil-solubility. However, since such reagents are sometimes used in a ratio of 1 to 10,000, or 1 to 20,000, or even 1 to 30,000, such an apparent insolubility in oil and water is'not significant, because said reagents undoubtedly.

have solubility within the concentration employed. This'same fact is true in regard to the material or materials herein described, except that they are invariably water-soluble.

We desire to point out that the superiority of the reagent or demulsitying agent contemplated in our herein described process for breakin petroleum emulsions, is based upon its ability .to treat certain emulsions more advantageously and a treating agent or demulsiiying agent of the" kind above described is brought into contact with or-caused to act upon the emulsion to be treated, in any of the various ways, or by any of the various apparatus now generally used to resolve or break petroleum emulsions with a chemical reagent,.the above procedure being used either alone, or in combination with other demulsifymg procedure, such as the electrical dehydration process.

The demulsifler herein contemplated may be employed in connection with what is commonly known as down-the-hole procedure, 1. e., bringing the demulsifler in contact with the fluids of the well at the bottom of the well, or at some point prior to their emergence. This particular type of application is decidedly feasible when the demulsifier is used in connection with acidification of calcareous oil-bearing strata, especially if suspended in or dissolved in the acid employed for acidification.

cognizance must be taken of the fact that the surface of the reacting vessel may increase or decrease reaction rate and degree of polymerization, for instance, an iron reaction vessel speeds up reaction and polymerization, compared with a glass-lined vessel.

' As has been previously indicated, the sub-genus employed as an alcohol in the present instance is'bne of a series of alcoholic compounds which are contemplated in our co-pending applications Serials Nos. 447,151, 447,152, 447,153, 447,154, 447,155, 447,156, 447,157, 447,158, 447,159, 447,160,

instance, but elaboration is eliminated, because it is unnecessary and would only incur greater length of descriptive matter. Thus, stated in another way, inall appropriate instances, the expression esteriflcation polymers in the appended claims, includes amidification polymers.

as well as esteriflcation polymers.

Having thus described our invention, what we claim as new and desire to secure by Letters Patent-is:

1. A process for breaking petroleum emulsions of the water-in-oil type, characterized by sub- Jecting the emulsion to the action of a demulsifler comprising a member of the class consisting of monomers, sub-resinous esterification polymers, andcogenerlc sub' resinous heat-rearranged derivatives of the monomers and afore-.

mentioned polymers, separately and jointly, and of the following formula V in which R is the carboxyl-free radical of a polybasic carboxy acid having not over 8 carbon atoms; R1 is a hydroxylated substituted pyridinium' halogen radical, containing as a substituent forwthe pyridinium hydrogen a radical containing at least. 8 and not more than 59 carbon atoms and having as an integral part thereof at least one alcoholic hydroxyl radical; Z is an acidic hydrogen atom equivalent including the acidic hydrogen atom itself; 11 represents the numerals 2 to 4; n represents the numerals 3 to 10; n" represents the, numerals 1 to 2; :2: represents the numerals to 2; yrepresents the numerals 0 to 2; 2 represents the numerals 1 to 3; :r' represents the numerals 0 to 1; and 1,! represents the numerals 1 to '2,

2. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifier comprising a member of the class consisting of monomers, sub-resinous esterification polymers, and cogeneric sub-resinous heat-rear ranged derivatives of the monomers and aforementioned polymers, separately and jointly, and

- of the following formula:

.n which R. is a carboxyl-free radical of a dibasic :arboxy acid having'not, over 6 carbon atoms; R1 is a hydroxylated substituted pyridinium halogen radical, containing as a substituent for the pyridinium hydrogen a radical containing at alcoholic hydroxyl radical; Z is an acidic hydrogen atomequivalent including the acidic hydrogen atom itself; n represents the numerals 2 to 4; n represents the numerals 3 to 10; :1: represents the numerals 0 to 2; 1! represents the numerals 0 to 2; andz represents the numerals l to. 3.

3. A process for breaking petroleum emulsions of the water-in-oil type, characterized bysub- 'jec'ting the emulsion to the action of a demulsifler I numerals 1 to 3.

carboxy acid having not over 6 carbon atoms; R1 is a hydroxylatedsubstituted pyridinium halogen radical, containing as a substituentfor thepyridinium hydrogen a radical containing at least 8 and not more than 59 carbon atoms and having as an integral part thereof atleast one alcoholic hydroxyl radical; Z is an acidic hydrogen atom equivalent including the acidic hydrogen atom itself; n represents thenumerals' 3 to 10; a: represents the numerals 0 to 2; .1! represents the numerals 0 to 2; and 2 represents the 4. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting. the emulsion to the action of a demulsifier comprising a polar, member of the class conleast '8 and not more than 59 carbon atoms and having as'an integral part thereof at least one alcoholic hydroxyl radical; Z is. an acidic hydrogen atom equivalent lncluding the acidic hydrogen atom itself; n" represents the numerals 3 t to 10; :1: represents the numerals 0 to 2; 1) repre-- sents the numerals 0 to 2; and 2 represents the "least 8 and not more than 59 carbon atoms and having as an integral part thereof atleast one comprising a member of the class consisting of monomers, sub-resinous esterification polymers,

and cogeneric sub-resinous heat-rearranged derivatives of the monomers and aforementioned polymers, separately and jointly, and of the fol lowing formula: J V

- llclmowoooacooz i clniowuclmowm,

' (c,'mo oocacooall.

numerals 1 to '3. i 1

5. A process for breaking petroleumemulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifier comprising a polar acidic member of the class consisting of monomers, sub-resinous esteriflcation polymers, and cogeneric sub-resinous heatrearranged derivatives of the monomers and aforementioned polymers, separately and jointly, andof the following formula:

in which R is a carboxyl-free radical of a dibas'ic carboxyacid having not over 6 carbon atoms; R1 is a hydroxylate'd substituted 'pyridinium halogen radical, containing as a substituent for the pyridinium hydrogen a radical containing at least 8 and not more than 59 carbon atoms 1 andhaving as an integral part thereof at least one alcoholic, hydroxyl radical; -Z is an acidic 7 hydrogen atom equivalent including thejacidic hydrogen atom itself; n' represents the numerals 3 to 10; :r'represents the numerals 0 to 2; zrrep'reiiiymcn a is a carboxyl-free radical or a dibaslic sents the-numerals 0 to 2; and .2 represents the numerals 1; to 3.

MELvmnE GROOTE BERNHARD KEISER. 

